CN104009224A - Method for synthesizing lithium iron silicate positive electrode material by using chrysotile asbestos as raw material - Google Patents
Method for synthesizing lithium iron silicate positive electrode material by using chrysotile asbestos as raw material Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 36
- 239000002994 raw material Substances 0.000 title claims abstract description 26
- CWBIFDGMOSWLRQ-UHFFFAOYSA-N trimagnesium;hydroxy(trioxido)silane;hydrate Chemical compound O.[Mg+2].[Mg+2].[Mg+2].O[Si]([O-])([O-])[O-].O[Si]([O-])([O-])[O-] CWBIFDGMOSWLRQ-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 10
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 title abstract description 5
- 230000002194 synthesizing effect Effects 0.000 title abstract description 3
- QSNQXZYQEIKDPU-UHFFFAOYSA-N [Li].[Fe] Chemical compound [Li].[Fe] QSNQXZYQEIKDPU-UHFFFAOYSA-N 0.000 title abstract 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000000203 mixture Substances 0.000 claims abstract description 22
- 239000010425 asbestos Substances 0.000 claims abstract description 21
- 229910052895 riebeckite Inorganic materials 0.000 claims abstract description 21
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 18
- 239000012298 atmosphere Substances 0.000 claims abstract description 15
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims abstract description 14
- 239000002243 precursor Substances 0.000 claims abstract description 14
- 238000001238 wet grinding Methods 0.000 claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract description 12
- 230000001681 protective effect Effects 0.000 claims abstract description 11
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 10
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 10
- 229910000272 alkali metal oxide Inorganic materials 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 7
- 239000012535 impurity Substances 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- 229910052744 lithium Inorganic materials 0.000 claims description 25
- 229910052620 chrysotile Inorganic materials 0.000 claims description 20
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 19
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 18
- ZNDKHNUDMXNQMF-UHFFFAOYSA-N [Li].[Fe].[Si](O)(O)(O)O Chemical compound [Li].[Fe].[Si](O)(O)(O)O ZNDKHNUDMXNQMF-UHFFFAOYSA-N 0.000 claims description 17
- 239000010405 anode material Substances 0.000 claims description 14
- 239000000835 fiber Substances 0.000 claims description 12
- 229910052710 silicon Inorganic materials 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- 239000004408 titanium dioxide Substances 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 3
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 3
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 claims description 3
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 150000003891 oxalate salts Chemical class 0.000 claims description 2
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 11
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 8
- 238000011161 development Methods 0.000 abstract description 4
- 239000002121 nanofiber Substances 0.000 abstract description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract description 3
- 239000011707 mineral Substances 0.000 abstract description 3
- 239000003929 acidic solution Substances 0.000 abstract 1
- 238000001816 cooling Methods 0.000 abstract 1
- 125000004122 cyclic group Chemical group 0.000 abstract 1
- 238000007598 dipping method Methods 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 238000004321 preservation Methods 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 238000007599 discharging Methods 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 230000004087 circulation Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 230000010354 integration Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000005543 nano-size silicon particle Substances 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- -1 ferrous oxalates Chemical class 0.000 description 2
- 239000008246 gaseous mixture Substances 0.000 description 2
- 229910052909 inorganic silicate Inorganic materials 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 229910000519 Ferrosilicon Inorganic materials 0.000 description 1
- 239000004277 Ferrous carbonate Substances 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- 229910013318 LiMSiO4 Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- 101000874049 Magnolia grandiflora Beta-cubebene synthase Proteins 0.000 description 1
- 229910018095 Ni-MH Inorganic materials 0.000 description 1
- 229910018477 Ni—MH Inorganic materials 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052599 brucite Inorganic materials 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- RAQDACVRFCEPDA-UHFFFAOYSA-L ferrous carbonate Chemical compound [Fe+2].[O-]C([O-])=O RAQDACVRFCEPDA-UHFFFAOYSA-L 0.000 description 1
- 229960004652 ferrous carbonate Drugs 0.000 description 1
- 235000019268 ferrous carbonate Nutrition 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000009970 fire resistant effect Effects 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000010903 husk Substances 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 229910000015 iron(II) carbonate Inorganic materials 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 229920000447 polyanionic polymer Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 229910021426 porous silicon Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000011833 salt mixture Substances 0.000 description 1
- 229910021487 silica fume Inorganic materials 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to a method for synthesizing a lithium iron silicate positive electrode material by using chrysotile asbestos as raw material, and belongs to the technical field of lithium ion battery. The method comprises the steps: placing the chrysotile asbestos in an acidic solution, carrying out acid dipping, then carrying out water washing, filtering and drying to obtain a silica nanofiber having alkali metal oxide impurities removed; carrying out wet grinding and even mixing of a lithium salt, a ferrous salt and the silica nanofiber obtained in the above steps to obtain a precursor mixture, under a protective atmosphere, tabletting the obtained precursor mixture, then carrying out heat preservation for 7-13 h under a condition of the temperature of 650 DEG C-800 DEG C, cooling to the room temperature, and thus obtaining the lithium iron silicate positive electrode material. The method has the advantages of simple process and low cost, and provides conditions for cyclic utilization of asbestos tailings of an asbestos mine and achieving of sustainable development of enterprise and mineral resources.
Description
Technical field
The present invention relates to a kind of method that Chrysotile is raw material synthetic silicic acid iron lithium anode material of take, belong to technical field of lithium ion.
Background technology
Fast development along with electronics and information industry, mobile communication, digital vedio recording and portable computer are used widely, the development of electric automobile and exploitation be also carrying out extensively and profoundly, thereby drive the developing rapidly of device-lithium ion battery that the energy is provided for the said equipment.Compare with nickel-cadmium cell with traditional Ni-MH battery, it is high that lithium ion battery has energy density, operating voltage is high, self discharge is little, can fast charging and discharging, the advantage such as security performance is good, be with fastest developing speed, a kind of secondary cell that market prospects are the brightest at present.
The performance that in lithium ion battery, battery material is determined to battery plays decisive influence effect.1996, Goodenough seminar proposed olivine-type LiFePO4 positive electrode first, and Armand proposes another kind of take the orthosilicate positive electrode that SiO4 tetrahedron is polyanion group, i.e. LiMSiO4(M=Fe, Mn etc. at patent US6085015).This type of positive electrode has stable SiO4 tetrahedron skeleton, abundant natural resources, advantages of environment protection, and in addition, it can allow 2 reversible de-embeddings of Li+ in theory, and theoretical capacity reaches 330mAh/g.But it is after discharging and recharging for the first time, and great changes will take place for structure, thereby affect the reversible de-embedding of lithium ion, hindered its application.In fact, the silicate anodal material that the ferric metasilicate lithium of take is representative can only take off 1 lithium ion of embedding in the use, causes its theoretical capacity only to have 166 mAh/g.At present, people by surface be coated, the method such as metal-doped and synthesizing nano-particle improves its chemical property, wherein carbon is coated is comparatively common method of modifying.
The silicon source of preparation high-performance silicic acid iron lithium mostly is nano silicon, expensive, is not suitable for large-scale production.The effective ways that address this problem adopt naturally occurring nano silicon as raw material exactly.For example, discarded object SILICA FUME when, Chinese patent CN102509776A proposes to take ferrosilicon enterprise and produces as silicon source, prepare high performance ferric metasilicate lithium; The silicon dioxide that Chinese patent CN103342369A and CN103346300A proposition are usingd in rice husk is as the method for silicon source synthetic silicic acid iron lithium.The present invention proposes a kind of nanometer titanium dioxide silica fibre in chrysotile is silicon source, prepares the method for high-performance silicic acid iron lithium, have advantages of cheap, be easy to large-scale production.
Chrysotile (Mg
6[Si
4o
10] (OH)
8) be a kind of natural nanofiber, its draw ratio is large, rich flexible, fire-resistant, alkaline-resisting, wear-resisting, and conductive coefficient is low, is a kind of desirable raw material of manufacturing heat-insulating material, also can be used as the filler of humidification simultaneously.Chrysotile belongs to silicates mineral, and its crystal structure elementary layer is comprised of one deck silicon-oxy tetrahedron and brucite octahedron.Because elementary layer is asymmetric, techonosphere bend form octahedra outside, tetrahedron is in interior socket columnar structure.Choysotile fiber external diameter is between 16～56nm, and interior warp is at 3.5～24nm.The OH that chrysotile fiber surface is a large amount of
-be easy to H
+reaction and cause Mg
2+exposed, at H
+in enough situations, MgO is also by complete stripping, and reaction equation is:
Mg
6[Si
4O
10](OH)
8+12H
+→6Mg
2++4SiO
2+10H2O。Choysotile Mian Kuang China reserves are large, and chrysotile, after overpickling leaches, can obtain nanometer titanium dioxide silica fibre.
Summary of the invention
The invention provides a kind of method of Chrysotile as raw material synthetic silicic acid iron lithium anode material of take, the present invention adopts the method for " from top to bottom ", Chrysotile prepared by the Natural Chrysotile of take is raw material, by its intermediary of pickling, see the nanoscale choysotile fiber in field, stripping MgO wherein, obtain fibrous nano silicon dioxide, using it as silicon source synthetic silicic acid iron lithium anode material.This method technique is simple, with low cost, by recycling asbestos tailings for asbestos mine, the sustainable development that realizes enterprise and mineral resources provides condition, the present invention is achieved through the following technical solutions.
The method that the Chrysotile of take is raw material synthetic silicic acid iron lithium anode material, its concrete steps are as follows:
(1) first by choysotile asbestos according to H
+concentration and choysotile asbestos mass ratio are that 0.025～0.05:1～2mol/g is placed in acid solution, in temperature, be acidleach 42～127min under 90～100 ℃ of conditions, then through washing, filtration with after being dried, obtain removing the silica nano fibrous of alkali metal oxide impurity;
(2) take ratio wet-milling that the nanometer titanium dioxide silica fibre of lithium salts, ferrous salt and step (1) gained is 2:1:1 as raw material according to the mol ratio of Li, Fe, Si and mix and obtain precursor mixture, in wherein wet-milling process, according to liquid-solid ratio 20ml/g～80ml/g, add ethanol or acetone;
(3) under protective atmosphere, after the precursor mixture compressing tablet that step (2) is obtained, in temperature, be to be incubated 7～13h under 650 ℃～800 ℃ conditions, obtain ferric metasilicate lithium positive electrode material after being cooled to room temperature.
Choysotile asbestos in described step (1) comprises following mass percent component: Si19～35%, Mg19～25%, Fe0.13～2.4%, Al0.03～0.32%, O42～53%.
Acid solution in described step (1) is sulfuric acid, nitric acid or hydrochloric acid.
Lithium source in described step (2) is one or several arbitrary proportion mixtures in lithium carbonate, lithium acetate, lithia, lithium hydroxide, lithium sulfate, lithium nitrate, lithium phosphate.
Ferrous salt is one or several arbitrary proportion mixtures in ferrous oxide, carbonate, acetate, oxalates in described step (2).
Protective atmosphere in above-mentioned steps (3) is under the atmosphere of nitrogen, argon gas, helium or their arbitrary proportion gaseous mixture.
The invention has the beneficial effects as follows: (1) of the present invention prepares in the method for porous silicon nanofiber/carbon composite, raw materials used aboundresources, production technology is simple, flow process is short, processing ease, equipment investment are little, can be used for the production of lithium ion battery; (2) nanometer titanium dioxide silica fibre is extracted in this invention from choysotile, as the raw material of lithium ion battery ferric metasilicate lithium positive electrode material, has widened the application of choysotile.
Embodiment
Below in conjunction with embodiment, the invention will be further described.
Embodiment 1
The method that the Chrysotile of should take is raw material synthetic silicic acid iron lithium anode material, its concrete steps are as follows:
(1) first by 1g choysotile asbestos according to H
+concentration and choysotile asbestos mass ratio are that 0.025:1mol/g is placed in acid solution, in temperature, be acidleach 127min under 96 ℃ of conditions, then through washing, filtration with after being dried, obtain removing the silica nano fibrous of alkali metal oxide impurity, wherein choysotile asbestos comprises following mass percent component: Si19%, Mg19%, Fe2.4%, Al0.29%, O42.3%;
(2) take ratio wet-milling that the nanometer titanium dioxide silica fibre of lithium salts, ferrous salt and step (1) gained is 2:1:1 as raw material according to the mol ratio of Li, Fe, Si mixes and obtains precursor mixture, in wherein wet-milling process, according to liquid-solid ratio 20ml/g, add ethanol, lithium source is lithium carbonate; Ferrous salt is ferrous oxalates;
(3) under protective atmosphere, after the precursor mixture compressing tablet that step (2) is obtained, in temperature, be to be incubated 7h under 800 ℃ of conditions, obtain ferric metasilicate lithium positive electrode material after being cooled to room temperature.
Protective atmosphere in above-mentioned steps (3) is under nitrogen atmosphere.
Ferric metasilicate lithium material obtained above is prepared into battery, concrete steps are as follows: resulting materials is mixed according to mass ratio 8:1:1 with conductive agent acetylene black, binding agent PVDF, with NMP by this mixture furnishing slurry, evenly be coated on the aluminium foil that thickness is 20 μ m, 80 ℃ of vacuumize 18h, make experiment positive plate.Take metal lithium sheet as negative pole, 1 mol/L LiPF
6eC/EMC (3:7) is electrolyte, and thermal isolation film is that barrier film is Celgard2400, in argon gas atmosphere glove box, is assembled into button cell.More than LAND battery charging and discharging test, carry out charge-discharge test, work system is: constant current charges and discharge, charging and discharging currents 1/16C, charging/discharging voltage are 1.5V～4.8V (vs.Li+/Li).The initial charge capacity 125mA/g of ferric metasilicate lithium, is 120.6mA/g after 20 circulations, and capability retention is 96.5%.
Embodiment 2
The method that the Chrysotile of should take is raw material synthetic silicic acid iron lithium anode material, its concrete steps are as follows:
(1) first by 10g choysotile asbestos according to H
+concentration and choysotile asbestos mass ratio are that 0.05:2mol/g is placed in acid solution, in temperature, be acidleach 100min under 90 ℃ of conditions, then through washing, filtration with after being dried, obtain removing the silica nano fibrous of alkali metal oxide impurity, wherein Si19%, Mg25%, Fe1.6%, Al0.32%, O53%, acid solution is hydrochloric acid;
(2) take ratio wet-milling that the nanometer titanium dioxide silica fibre of lithium salts, ferrous salt and step (1) gained is 2:1:1 as raw material according to the mol ratio of Li, Fe, Si mixes and obtains precursor mixture, the ethanol adding according to liquid-solid ratio 80ml/g in wherein wet-milling process, lithium source is lithium acetate, and ferrous salt is ferrous oxalates;
(3) under protective atmosphere, after the precursor mixture compressing tablet that step (2) is obtained, in temperature, be to be incubated 13h under 650 ℃ of conditions, obtain ferric metasilicate lithium positive electrode material after being cooled to room temperature.
Protective atmosphere in above-mentioned steps (3) is under the atmosphere of argon gas.
According to method identical in embodiment 1, carry out the Integration Assembly And Checkout of battery, test result: the initial charge capacity of ferric metasilicate lithium material is 120mAh/g, after 20 circulations, charging capacity is 116.4mAh/g, and capability retention is 97%.
Embodiment 3
The method that the Chrysotile of should take is raw material synthetic silicic acid iron lithium anode material, its concrete steps are as follows:
(1) first by 10g choysotile asbestos according to H
+concentration and choysotile asbestos mass ratio are that 0.03:1mol/g is placed in acid solution, in temperature, be acidleach 42min under 98 ℃ of conditions, then through washing, filtration with after being dried, obtain removing the silica nano fibrous of alkali metal oxide impurity, wherein choysotile asbestos comprises following mass percent component: Si27%, Mg22%, Fe0.13%, Al0.03%, O48%, and acid solution is sulfuric acid;
(2) take ratio wet-milling that the nanometer titanium dioxide silica fibre of lithium salts, ferrous salt and step (1) gained is 2:1:1 as raw material according to the mol ratio of Li, Fe, Si mixes and obtains precursor mixture, in wherein wet-milling process, according to liquid-solid ratio 60ml/g, add acetone, lithium salts is that lithium hydroxide, ferrous salt are ferrous oxide;
(3) under protective atmosphere, after the precursor mixture compressing tablet that step (2) is obtained, in temperature, be to be incubated 10h under 700 ℃ of conditions, obtain ferric metasilicate lithium positive electrode material after being cooled to room temperature.
Protective atmosphere in above-mentioned steps (3) is that volume ratio is under the nitrogen of 1:1 and the atmosphere of argon gas gaseous mixture.
According to method identical in embodiment 1, carry out the Integration Assembly And Checkout of battery, test result: the initial charge capacity of ferric metasilicate lithium material is 132mAh/g, after 20 circulations, charging capacity is 125.7mAh/g, and capability retention is 95.2%.
Embodiment 4
The method that the Chrysotile of should take is raw material synthetic silicic acid iron lithium anode material, its concrete steps are as follows:
(1) first by 10g choysotile asbestos according to H
+concentration and choysotile asbestos mass ratio are that 0.04:1mol/g is placed in acid solution, in temperature, be acidleach 60min under 100 ℃ of conditions, then through washing, filtration with after being dried, obtain removing the silica nano fibrous of alkali metal oxide impurity, wherein choysotile asbestos comprises following mass percent component: Si35%, Mg20%, Fe1.3%, Al0.18%, O42%, and acid solution is nitric acid;
(2) take ratio wet-milling that the nanometer titanium dioxide silica fibre of lithium salts, ferrous salt and step (1) gained is 2:1:1 as raw material according to the mol ratio of Li, Fe, Si mixes and obtains precursor mixture, in wherein wet-milling process, add according to liquid-solid ratio 50ml/g and add ethanol, lithium salts is the lithium salts mixture of lithia, lithium sulfate, lithium nitrate and the lithium phosphate of mass ratio 1:1:1:1, and ferrous salt is the ferrous carbonate of mass ratio 1:1 and the ferrous salt mixture of acetate;
(3) under protective atmosphere, after the precursor mixture compressing tablet that step (2) is obtained, in temperature, be to be incubated 6h under 700 ℃ of conditions, obtain ferric metasilicate lithium positive electrode material after being cooled to room temperature.
According to method identical in embodiment 1, carry out the Integration Assembly And Checkout of battery, test result: the initial charge capacity of ferric metasilicate lithium material is 127mAh/g, after 20 circulations, charging capacity is 122.3mAh/g, and capability retention is 96.3%.
Claims (5)
1. the method that the Chrysotile of take is raw material synthetic silicic acid iron lithium anode material, is characterized in that concrete steps are as follows:
(1) first by choysotile asbestos according to H
+concentration and choysotile asbestos mass ratio are the acid solution that 0.025～0.05:1～2mol/g is placed in, in temperature, be acidleach 42～127min under 90～100 ℃ of conditions, then through washing, filtration with after being dried, obtain removing the silica nano fibrous of alkali metal oxide impurity;
(2) take ratio wet-milling that the nanometer titanium dioxide silica fibre of lithium salts, ferrous salt and step (1) gained is 2:1:1 as raw material according to the mol ratio of Li, Fe, Si and mix and obtain precursor mixture, in wherein wet-milling process, according to liquid-solid ratio 20ml/g～80ml/g, add ethanol or acetone;
(3) under protective atmosphere, after the precursor mixture compressing tablet that step (2) is obtained, in temperature, be to be incubated 7～13h under 650 ℃～800 ℃ conditions, obtain ferric metasilicate lithium positive electrode material after being cooled to room temperature.
2. according to claim 1ly take the method that Chrysotile is raw material synthetic silicic acid iron lithium anode material, it is characterized in that: the choysotile asbestos in described step (1) comprises following mass percent component: Si19～35%, Mg19～25%, Fe0.13～2.4%, Al0.03～0.32%, O42～53%.
3. according to claim 1ly take the method that Chrysotile is raw material synthetic silicic acid iron lithium anode material, it is characterized in that: the acid solution in described step (1) is sulfuric acid, nitric acid or hydrochloric acid.
4. according to claim 1ly take the method that Chrysotile is raw material synthetic silicic acid iron lithium anode material, it is characterized in that: the lithium source in described step (2) is one or several arbitrary proportion mixtures in lithium carbonate, lithium acetate, lithia, lithium hydroxide, lithium sulfate, lithium nitrate, lithium phosphate.
5. according to claim 1ly take the method that Chrysotile is raw material synthetic silicic acid iron lithium anode material, it is characterized in that: in described step (2), ferrous salt is one or several arbitrary proportion mixtures in ferrous oxide, carbonate, acetate, oxalates.
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